CN1637092A - Solid radiation-curable binders with reactive diluents - Google Patents
Solid radiation-curable binders with reactive diluents Download PDFInfo
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- CN1637092A CN1637092A CNA2004100982745A CN200410098274A CN1637092A CN 1637092 A CN1637092 A CN 1637092A CN A2004100982745 A CNA2004100982745 A CN A2004100982745A CN 200410098274 A CN200410098274 A CN 200410098274A CN 1637092 A CN1637092 A CN 1637092A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/934—Powdered coating composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Powder coating binders having a glass transition temperature of > 35 ℃, comprising at least one polymer and one or more radiation-curable reactive diluents, a process for producing these powder coating binders and their use as powder coating components.
Description
CROSS-REFERENCE TO RELATED PATENT
According to 35U.S.C. § 119 (a)-(d), present patent application requires the right of priority of the German patent application No.10356041.6 of proposition on December 1st, 2003.
Technical field
The present invention relates to novel powder paint substrate, its second-order transition temperature 〉=35 ℃, comprise at least a organic polymer and one or more radiation curing reactive diluents, be used to produce the method and they purposes of these powder paint substrates as the powder coating component.
Background technology
Powder paint substrate is applied on the base material, utilizes heating and melting, and is cured by radiation curing, electromagnetic radiation.In recent years, more and more important by means of the curing of electromagnetic radiation.This solidification process is very fast, and this has reduced the process speed that applies operation and has therefore saved expense.Radiation curable powder coating prolonged well known (US-A3,974,30 3), and normally based on polyester (for example DE-A4228514), urethane (EP-A410242) and polyacrylic ester (DE-A4413436).Mixture also is known.
Use low polyurethane(s) and polyurethane(s) can obtain special fine coating as powder binder.Though EP-A410242 has described and produced these base-materials in organic solvent, but DE-A19939843 has instructed solvent-free production method, wherein used the crystallographic component of 10 to 95% high weight ratio, described crystallographic component by single-or vulcabond and monohydroxy alkyl (methyl) acrylate form.This synthetic method without solvent only can be used for by means of the viscosity-reduction of fusion-crystallization component implementing.
The low polyurethane(s) of describing among EP-A410242 and the DE-A19939843 and the shortcoming of polyurethane(s) are the grindability indexs of their differences.Can only under 0 ℃ the temperature product be ground and do not form agglomerate being lower than, and all other powder treatment processes must be carried out under subambient temperature.
Under the amorphous material situation, whether their character be studied decision being higher or lower than under its second-order transition temperature by this material.Below the second-order transition temperature, obtain triturable product at it usually.If second-order transition temperature is too high, product can only be stirred under very high temperature.The character of powder coating depends on the envrionment temperature during powder coated to a great extent.In summer, especially near with the needed baking oven of powder coating fusion, can will be higher than 20 to 25 ℃ common room temperature by estimating temperature.Therefore, in fact, for powder coating, the sufficiently high second-order transition temperature that is higher than 35 ℃ is necessary.
Described ultraviolet powder paint substrate in PCT application WO03/044111, it is unbodied and has low especially viscosity under molten state.Use for some, the high molecular of urethane acrylate is disadvantageous.Therefore, almost there is not leeway to regulate two key density.
In the ultraviolet liquid paint chemistry, common be to use so-called reactive diluent, reduce the viscosity of liquid paint on the one hand, improve ultraviolet reactive behavior by improving two key density simultaneously, it is also relevant with the paint tolerance value that improves usually.
Therefore, the purpose of this invention is to provide the radiation curing powder, this radiation curing powder can at room temperature be ground, has the long shelf-life, and the tendency that under working condition and the processing conditions relevant, does not have caking with reality, this radiation curing powder can be produced without solvent, and opposite with prior art, comprises the reactive diluent that is used to regulate two key density usually in the liquid paint chemistry.
Summary of the invention
The present invention relates to powder paint substrate, this powder paint substrate has at least 35 ℃ second-order transition temperature, comprise at least a following organic polymer that is selected from: polyurethane(s), polyester, polyacrylic ester, polyethers, polymeric amide, polycarbonate and above-mentioned mixture of polymers, and one or more radiation curing reactive diluents of at least 2 weight percentage.
The present invention also provides the method for producing above-mentioned powder paint substrate, and it comprises the following component of mixing:
A) one or more are selected from following organic polymer: polyurethane(s), polyester, polyacrylic ester, polyethers, polymeric amide, polycarbonate and composition thereof; With
B) one or more radiation curing reactive diluents of at least 2 weight %,
Wherein component a) and b) composition, and the quantification between them is selected such that the second-order transition temperature of the powder paint substrate that obtains is at least 35 ℃.
The present invention also provides powder coating, and it comprises:
I) powder paint substrate of at least a claim 1,
Ii) other unsaturated base-materials randomly, this unsaturated base-material is different from i), have the group (radiation cure groups) that can react by polymerization under the actinic radiation effect and alefinically unsaturated compounds,
Iii) common auxiliary substance and additive in the paint chemistry randomly, its be selected from pigment, flowing regulator, air release agent, friction active additive and/or thixotropic agent and
Iv) at least a thermal activation or photochemistry activatory free radical form agent.
The present invention also provides the method for coated substrate, it comprises above-mentioned powder paint substrate and powder coating is coated at least a portion of base material, the invention still further relates to the coating that obtains from above-mentioned powder paint substrate and powder coating, and with the base material of this coating coating.
Detailed Description Of The Invention
Except the situation among the operation embodiment, perhaps indicated in addition, the numeral or the expression of the amount of using in specification sheets and the claim all about composition, reaction conditions or the like should be understood that all to be modified by term " approximately " in all instances.
The invention provides the radiation curing powder, it can at room temperature be ground, and has the long shelf-life, and does not have the tendency of caking under working condition and the processing conditions relevant with reality.This powder can be produced without solvent, and comprises the reactive diluent that is used to regulate two key density usually in the liquid paint chemistry.
Therefore, have been found that in the present invention, if use to be fit to, undersaturated organic polymer randomly, one or more reactive diluents have been added extraly although make, still obtain having the mixture of enough high glass-transition temperatures, then in having the melt of solvent, also can not produce the powder that is easy at room temperature be ground and have the long shelf-life.
This is wonderful, because when adding reactive diluent, estimate that usually second-order transition temperature will obviously reduce, or even formation agglomerate.
The invention provides powder paint substrate, it has at least 35 ℃ second-order transition temperature, comprise at least a following organic polymer that is selected from: polyurethane(s), polyester, polyacrylic ester, polyethers, polymeric amide, polycarbonate and above-mentioned mixture of polymers, and one or more radiation curing reactive diluents of at least 2 weight percentage.
The present invention also provides the method for production powder paint substrate of the present invention, wherein
A) one or more are selected from following organic polymer: polyurethane(s), polyester, polyacrylic ester, polyethers, polymeric amide, polycarbonate and above-mentioned mixture of polymers, at its production period or afterwards, with
B) one or more radiation curing reactive diluents of at least 2 weight % mix,
Wherein component a) and b) composition and their mutual quantifications be selected such that the second-order transition temperature of base-material of the present invention is at least 35 ℃.
The present invention also provide method that powder paint substrate is added powder coating with and be used for the purposes of coated substrate, described base material is timber, metal, plastics, mineral substance and/or coated above-mentioned base material or the above-mentioned base material of being made up of any combination of described material.Use at this industrial coating that should mention especially and to comprise: MDF plate coating, preassembled high-grade goods (for example comprise for example be temperature-sensitivity those of structure unit) the coating of coating, automobile, car body and accessory thereof of coating, coatings for furniture, coil coating, daily life goods.But the also intermingling use of powder paint substrate with reactive diluent of the present invention perhaps mixes use with other base-materials that are generally used for the powder coating chemistry; For example mix use with polyester, polyacrylic ester, polyurethane(s), polyethers, polymeric amide and polycarbonate, it can also randomly comprise unsaturated group.
As common in polymer science, second-order transition temperature or second-order transition temperature (Tg) are described a kind of like this temperature, under this temperature, amorphous material is converted into liquid state (under the low molecular weight substance situation) or rubbery state (under the high molecular weight material situation) from vitreous state under heating.Those semi-crystalline materials also has second-order transition temperature.The details of this notion are found in H.-G.Elias, and polymer science is crossed the threshold (An Introduction to PolymerScience), VCH Verlagsgesellschaft mbH, Weinheim, Germany, 1997, the 315-316 pages or leaves.
Actinic radiation is understood to mean electromagnetism, ionizing rays, particularly electron beam, ultraviolet ray and visible light (Roche Lexikon Medizin, the 4th edition; Urban ﹠amp; Fischer Verlag, Munich, 1999).
Group (radiation cure groups) by the reaction of polymerization and alefinically unsaturated compounds under the actinic radiation effect can be for example vinyl, vinyl ether, propenyl, allyl group, maleinyl, fumaryl, maleimide, dicyclopentadienyl, acrylamide, acrylic acid or the like and methacrylic group, therein ethylene base ether, acrylic acid or the like and/or methacrylic group are preferred, and acrylic groups is particularly preferred.
In meaning of the present invention, reactive diluent refers to that all comprise average at least one radiation cure groups, and promptly at least one is by the organic substance of the group of polymerization under the actinic radiation effect and alefinically unsaturated compounds reaction.
Reactive diluent known to the skilled in radiation curing base-material chemical field is (referring to " being used for the UV of coating, printing ink and paint and the chemistry and technology (the Chemistry ﹠amp of EB preparation; Technology of UV ﹠amp; EB Formulations for Coatings, Inks ﹠amp; Paints) ", the 2nd volume, PKT Oldring (editor), SITA Technology, London, Britain, 250-290 page or leaf, 1991) except radiation curing functional group, do not have other functional groups usually.Yet, also very may use those compounds that comprise following group in addition: alcohol, acid, isocyanic ester, epoxy group(ing), silyl, phosphine, phosphoric acid ester, isocyanic ester, urea, isocyanuric acid ester, uretdione, biuret or other groups, particularly when can obtain other favourable effects whereby, all the more so during as binding property.
The example of reactive diluent is (methyl) vinylformic acid and ester thereof, (methyl) vinylformic acid vinyl ester, (methyl) vinylformic acid allyl ester, trimethylolpropane allyl ether, glycerol three (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate, neo-pentyl two (methyl) acrylate, vinylbenzene, Vinylstyrene, Vinyl toluene, isobornyl (methyl) acrylate, (methyl) butoxyethyl acrylate, aklylene glycol two (methyl) acrylate such as ethylene glycol and propylene glycol two (methyl) acrylate, polyalkylene glycol two (methyl) acrylate such as polyoxyethylene glycol and polypropylene glycol two (methyl) acrylate, two (methyl) acrylate such as butyleneglycol two (methyl) acrylate of simple glycol, hexylene glycol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, two cyclopentyl (methyl) acrylate.Preferably: hexanediyl ester, IBOMA, methacrylic acid isodecyl ester, tristane dimethanol dimethacrylate, tripropylene glycol diacrylate and ethoxylation or propoxylation glycol or polyvalent alcohol (methyl) acrylated product of TriMethylolPropane(TMP), tetramethylolmethane, dihydroxyphenyl propane or cyclohexanedimethanol for example randomly.
Can also use the mixture of above-claimed cpd.Preferably trimethylolpropane trimethacrylate and/or Viscoat 295.
If reactive diluent is used to produce base-material (for example from carbamate production) based on isocyanic ester; then preferably do not contain the reactive diluent that has reactive group with isocyanic ester, perhaps contain and the isocyanate reaction reactive diluent of group (as sterically hindered alcohol) very slowly.
The maximum level of reactive diluent reduces the degree decision of the second-order transition temperature of base-material by it.The second-order transition temperature of powder paint substrate of the present invention is generally 〉=and 35 ℃, preferred 〉=42 ℃ and preferred especially 〉=48 ℃.
Therefore preferably comprise the powder paint substrate that is less than 50 weight % and especially preferably is less than the radiation curing reactive diluent of 30 weight %.
Organic polymer preferably has 1000 to 10000g/mol, especially preferably has 1200 to 5000g/mol number-average molecular weight used according to the present invention.
The organic polymer of the above-mentioned type can be included under the actinic radiation effect unsaturated group (radiation cure groups) by polymerization and alefinically unsaturated compounds reaction or they can not contain these radiation cure groups used according to the present invention.Preferably, at least a per molecule of organic polymer comprises one or more radiation cure groups used according to the present invention.
Produce of the present inventionly have at least 35 ℃ Tg, the powder paint substrate that comprises one or more radiation curing reactive diluents of at least 2 weight % can carry out according to following process: at first prepare one or more organic polymers that the present invention uses, described organic polymer randomly is the form of mixture, adds then and the hybrid reaction thinner.Can also the production period of organic polymer or its mixture or even when the production of organic polymer or its mixture begins, add reactive diluent, its advantage is that the melt viscosity of mixture can be reduced.
Polyester that the present invention uses and polymeric amide normally pass through those of unsaturated acid or acid anhydrides formation.The typical initial substance that is used for this purpose is toxilic acid (acid anhydrides) and fumaric acid.
In order to form the organic polymer based on polyester, polycarbonate or polyurethane(s) and saturated alcohol used in the present invention, can also use unsaturated materials, as having (methyl) acrylic acid hydroxy alkyl ester of 2 to 12 carbon atoms, preferred 2 to 4 carbon atoms in the alkyl chain in the hydroxyalkyl residue, as (methyl) hydroxyethyl acrylate, (methyl) vinylformic acid 2-and 3-hydroxypropyl ester and (methyl) vinylformic acid 2-, 3-and 4-hydroxybutyl ester, and the functional vinyl ether of OH-, as hydroxybutyl vinyl ether and composition thereof.Can also use functional (methyl) acrylate of OH-or the acid amides of positive hydroxyl alcohol or amine or amino alcohol according to the present invention, and composition thereof.These compounds or product mixture comprise for example ester of glycerol, TriMethylolPropane(TMP) and/or tetramethylolmethane.Can also use from the monohydroxy-alcohol of epoxy functionalized (methyl) acrylate with the qualification of (methyl) acrylic acid reaction.For example, glycidyl methacrylate and acrylic acid reaction provide the vinylformic acid-methacrylic ester of blended glycerol, and it also can advantageously be used.
The vinylformic acid hydroxypropyl ester of hydroxyethyl acrylate and isomery is preferred.Because the production temperature height of polyester and polymeric amide, therefore, only for the preparation of polyurethane(s), the process of this use vinylformic acid-functional alcohol is preferred.
Polyacrylic ester can only carry out modification by radiation curing after the polymerization of acrylate and vi-ny l aromatic monomers.This realizes by means of the functional group that is inert under the working condition of polyacrylic ester.The possible group that can be modified on polyacrylic ester is:
| Functional group on the polyacrylic ester | Properties-correcting agent |
| Epoxy group(ing) | Vinylformic acid, propylene dimer acid |
| Acid | Glycidyl compound, for example glycidyl methacrylate |
| Alcohol | Vinylformic acid, propylene dimer acid |
| Alcohol | Vinylformic acid-functional isocyanate |
| Vinylformic acid, propylene dimer acid | Alcohol |
| Vinylformic acid-functional isocyanate | Alcohol |
| Acid anhydrides | Alcohol |
| Alcohol | Acid anhydrides |
Can also use the polyester of second-order transition temperature＞40 ℃.As well known by persons skilled in the art, these are produced from pure and mild acid in condensation reaction.In producing unsaturated polyester, use unsaturated diacid or acid anhydrides in addition, as fumaric acid and toxilic acid.About the detail file of this theme, with reference to European patent application EP 585742A1, page 1 the 30th row is to page 3 the 18th row.
Therefore, for example, reactive diluent can be added in the unsaturated polyester of the high glass-transition temperature with 57 ℃, as Uvecoat 2100 (from UCB Chemicals, Belgian commerical prod), can not reaching for the shelf-life is crucial lowest glass transition temperature.
The example based on the unsaturated organic polymer of polyurethane(s) that the present invention uses can be applied for WO03/044111 according to PCT, and the reaction by following material prepares:
A) one or more two-or polyisocyanates or its mixture, wherein randomly add monoisocyanates, with
B) one or more and isocyanic ester carry out multifunctional reaction compound and
C) one or more and isocyanic ester carry out the compound of monofunctional reactant,
Wherein, substance A) amount (NCO group mole number) and and the constituent substance B of isocyanate reaction) and the ratio of amount sum C) between 0.8 and 1.2; and (methyl) acryl group is included in B) or C) or in two kinds of components; it is characterized in that; at monofunctional compound C) go up with the equivalent of the group of isocyanate reaction with at multifunctional reactive compounds B) the normal ratio of the group of last and isocyanate reaction is less than 1.2; and the compd B that carries out multifunctional reaction with isocyanic ester) have on average functionality less than 2.5, and two-or the polyfunctional isocyanate in and with two of isocyanate reaction-or multifunctional component in the part by weight of soft group less than 25 weight %.
According to the present invention, the same with situation common in chemical language usage, the relative number of the reactive group that exists during term equivalent (Eq.) refers to react.According to the present invention, these are the groups with isocyanate reaction, as alcohol or amine.For example, under pure situation, when using 1 mole of monohydroxy-alcohol=1 equivalent and 1 mole of dibasic alcohol (i.e. 2 moles of OH groups)=2 equivalents, provide such ratio: 1Eq.: 2Eq.=0.5 according to the present invention.
The arithmetical mean of the molar fraction of compound that desired term in the description of the invention " carries out the average functionality of the compound of multifunctional reaction with isocyanic ester " and be meant carrying out multifunctional reaction with isocyanic ester after with its functionality weighting.For example, if use 1 mole of trimethylol propane (functionality 3) and 2 moles of ethylene glycol (functionality 2), the average functionality that provides is 1 mole/(1 mole+2 moles) 3+2 mole/(1 mole+2 moles) 2=2.33.
Desired term in the description of the invention " part by weight of soft group " is meant the chemical substructure in bifunctional structure component at least.These chemical substructures comprise:
1.) methylene group (the CH of acyclic
2-),
2.)-CHR-,-CR
2-group, it has the group that Sauerstoffatom adjacent thereto and/or methylene group and R represent to have no more than 16 carbon atoms exclusively, and it does not relate to urethane (urethanisation)/ureogenesis reaction,
3.) ether oxygen atom,
4.) thioether sulphur atom,
5.) two-and/or the polysulfide methylthio group,
6.)-O-S (Me)
2-O-group and
7.) olefin group (CH=CH-).
Independent, at least the part by weight of the soft group in the bifunctional structure component for example calculates according to following: for hexylene glycol, part by weight as 6 methylene groups and molecule gross weight calculate (this: 6 * 14/118=71%), for isophorone diisocyanate (1 acyclic methylene group=14/222=6.3%), for glycol ether (4 methylene groups, 1 ether oxygens: (4 * 14+1 * 16)/106=67.9%), for propylene glycol (1 methylene group, one by methyl substituted CHR group: (14+ (15+13))/76=55.2%), (there is not soft group for the Tolylamine vulcabond, promptly 0%), or the like.According to the present invention, in urethane acrylate the part by weight of soft group now by the part by weight of bifunctional structure component at least, in each case with aforesaid its soft ratio content weighting and calculate.
Isocyanic ester A) can be aliphatic series or aromatics: NSC 87419, butyl isocyanate, phenylcarbimide, TI, 1,4-butylidene vulcabond, 1,6-hexylidene diisocyanate (HDI), 1, the 8-inferior octyl diisocyanate, 1, the inferior undecyl vulcabond of 11-, 1, the inferior dodecyl vulcabond of 12-, 2,2,4-and 2,4,4-trimethylammonium-1,6-hexylidene diisocyanate (TMDI), 1,3-and 1, the 4-cyclohexyl diisocyanate, 1-isocyanato--3-isocyanato-methyl-3,5,5-trimethyl-cyclohexane (IPDI), 1-isocyanato--1-methyl-4 (3)-isocyanato-methylcyclohexane (IMCI), 1, the 4-phenylene vulcabond, 1, the 5-naphthalene diisocyanate, 1-isocyanato--2-isocyanato-methyl-pentamethylene, (4,4 '-and/or 2,4 '-) two isocyanato-dicyclohexyl methyl hydride (H12-MDI, W) two (4-isocyanato--3-methylcyclohexyl) methane, eylylene diisocyanate (XDI), tetramethyl--1,3-and/or-1,4-eylylene diisocyanate (TMXDI), 1,3-and/or 1,4-six hydrogen eylylene diisocyanates (H6-XDI), 2,4-and/or 2,6-methylcyclohexane diisocyanate (H6-TDI), 2,4-and/or 2,6-tolylene diisocyanate (TDI), 4,4 '-and/or 2,4 '-'-diphenylmethane diisocyanate (MDI), perhaps itself and carbamate, isocyanuric acid ester, allophanate, biuret, uretdione, the derivative of imidoyl-oxadiazine-diketone structural unit, condition is that they have at least one free NCO group, and composition thereof.IPDI, TDI, H12-MDI, H6-XDI and composition thereof are preferred.TDI, IPDI and H12-MDI are particularly preferred.
B component) can be polyvalent alcohol, ethylene glycol for example, 1,2-and 1, ammediol, various isomer butyleneglycols, neopentyl glycol, 1, the 6-hexylene glycol, the 2-methyl isophthalic acid, ammediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 2-normal-butyl-2-ethyl-1, ammediol, glycerol strand alkanoic acid ester (for example glyceryl monostearate), the dimer Fatty Alcohol(C12-C14 and C12-C18), glycol ether, triglycol, Tetraglycol 99,1,4-dihydroxymethyl-hexanaphthene, dodecanediol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, 1, the 3-hexylene glycol, 1, the 3-ethohexadiol, 1, the 3-decanediol, the 3-methyl isophthalic acid, the 5-pentanediol, 3,3-dimethyl-1,2-butane-glycol, the 2-methyl isophthalic acid, the 3-pentanediol, 2-methyl-2, the 4-pentanediol, 3-methylol-4-enanthol, 2-methylol-2,3-dimethyl-1-amylalcohol, glycerol, trimethylolethane, TriMethylolPropane(TMP), the tripolymer Fatty Alcohol(C12-C14 and C12-C18), the isomer hexanetriol, Sorbitol Powder, tetramethylolmethane, two (TriMethylolPropane(TMP)s), Dipentaerythritol, Glycerol dimer and tricyclo-decane (TCD).
Can also use according to the present invention can ester by OH-officials above-mentioned polyvalent alcohol and 6-caprolactone prepared in reaction, number-average molecular weight Mn＜2000, preferred Mn＜500.Except that above-mentioned alcohol, can also use the unsaturated ester of forming by unsaturated acid or alcohol, for example: toxilic acid (acid anhydrides), fumaric acid, methylene-succinic acid, citraconic acid (acid anhydrides), equisetic acid, tetrahydrophthalic acid (acid anhydrides), 3, in the 6--methylene radical-1,2,3,6-tetrahydrophthalic acid (acid anhydrides).
It is same that what be fit to is to comprise the alkohol and amine of (methyl) acryl group or basically by these reaction product of forming; they prepare by positive hydroxyl alcohol or amine or amino alcohol and the condensation of (methyl) vinylformic acid, can also use mixture as described alcohol, amine or amino alcohol.These compounds or product mixture comprise for example lower molecular weight alkoxylation products, for example ethoxylation or the propoxylation TriMethylolPropane(TMP) and (methyl) acrylic acid reaction product of glycerol, TriMethylolPropane(TMP) and/or tetramethylolmethane, this class alcohol.
According to the present invention, also use and additionally be incorporated in the urethane acrylate and group isocyanate reaction, dimethylol propionic acid (DMPA) for example, N methyldiethanol amine, the N-ethyldiethanolamine, N-(uncle)-butyl diethanolamine, N-sec.-propyl diethanolamine, N-n-propyl-diethanolamine, N-hexyl diethanolamine, the N-phenyldiethanol-amine, N-benzyl-diethanolamine, N-tolyl diethanolamine, N-lauryl diethanolamine, N-stearyl diethanolamine, trolamine, three (2-aminoethyl) amine, N, two (2-hydroxyl-ethyl) quadrols of N-, 2-(2-dimethyl aminoethyl amino) ethanol, 2-(2-diethyl-aminoethylamino) ethanol, two-2-(methylamino ethyl) methylamine and 1,4,7-triethyl-diethylenetriamine.Also randomly prepare the mixture of different urethane acrylates, it comprises DMPA on the one hand, comprises above-mentioned tertiary amine on the other hand.
Replace polyvalent alcohol or combine with polyvalent alcohol, can also produce the urea acrylate with following amine: thanomin, N-Mono Methyl Ethanol Amine, N-ehtylethanolamine, 2-amino-1-propyl alcohol, tetramethyl-xylylene amine, quadrol, 1,6-hexanediamine, isophorone diamine (IPDA), (4,4 '-and/or 2,4 '-) diamino-dicyclohexyl methyl hydride, (4,4 '-and/or 2,4 '-) diamino-3,3 '-dimethyl dicyclohexyl methyl hydride.
What all were mentioned has reactive difunctionality or all right form of mixtures use of multifunctional material with isocyanic ester.
Ethylene glycol, 1,2-and 1, ammediol, isomer butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 2-ethyl-1,3-hexylene glycol, perhydro bis-phenol and 4,8-two (methylol) three ring [5.2.0 (2.6)]-decane (TCD alcohol) are preferred.Ethylene glycol, 1,2-propylene glycol and 1, the 4-butyleneglycol is particularly preferred.
Be suitable as component C) be aliphatic series and aromatic alcohols, for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, hexanol, Fatty Alcohol(C12-C14 and C12-C18), phenol or the like, and especially, hydroxyalkyl (methyl) acrylate that in the hydroxyalkyl residue, in alkyl chain, has 2 to 12 carbon atoms, preferred 2 to 4 carbon atoms, for example (methyl) hydroxyethyl acrylate, (methyl) vinylformic acid 2-and 3-hydroxypropyl ester and (methyl) vinylformic acid 2-, 3-and 4-hydroxybutyl ester, and OH-functional vinyl ether, hydroxybutyl vinyl ether for example, and composition thereof.
As component C) can also use average 0.3-1.5-functional (methyl) acrylate of OH-doubly or the acid amides of positive hydroxyl alcohol or amine or amino alcohol, can also use mixture.These compounds or product mixture comprise for example ester of glycerol, TriMethylolPropane(TMP) and/or tetramethylolmethane.The monohydroxy-alcohol of regulation can also obtain from epoxy functionalized (methyl) acrylate and the reaction of (methyl) vinylformic acid.For example, glycidyl methacrylate and acrylic acid reaction provide the vinylformic acid-methacrylic ester of blended glycerol, and it also can advantageously be used.
The vinylformic acid hydroxypropyl ester of hydroxyethyl acrylate and isomery is preferred.
The reaction of hydroxy-functional acrylic ester and isocyanic ester is known, for example sees P.K.T.Oldring (editor), Chemistry and Technology of UV ﹠amp; EB Formulationsfor Coatings, Inks ﹠amp; Paints, the 2nd volume, 1991, SITA Technology, London, D.73-97.
Described preparation can be carried out according to following process: use the component A that comprises isocyanic ester 1.)) and make it and B) and C) reaction, this by with oxygen-containing gas, preferred air under the temperature of fusing point that is higher than the product that will produce or softening temperature, in 30 to 150 ℃, preferred 70 to 130 ℃, preferred especially 80 to 120 ℃ temperature range, undertaken by them, be reduced to desirable value up to NCO content, the NCO that is using: under OH ratio=1 situation, be reduced to and preferably be lower than 0.3 weight %, especially preferably be lower than 0.1 weight %.During this technology, what come in handy is 2.) be metered into B dividually or as mixture in succession independently, simultaneously) and C).Preferably measure them as mixture.
Can also 3.) get B) and C) and be metered into A).The 4th kind of process at first got B), be metered into C then), add A at last), also may be favourable.5.) 4.) in A) and order B) can be reversed.Scheme 1) be particularly preferred.
Reactive diluent preferably adds initial component in the initial stage, but also can be metered into later on.(partly) with isocyanic ester have reactive reactive diluent preferably with B) and/or C) introduce reaction mixture.Can also only afterwards reactive diluent be added A), B) and C) or A) and B) or A) and the product of partial reaction C) in.Can also carry out follow-up adding, randomly add by extruding.Preferably when synthetic beginning, add reactive diluent.
Production of polyurethane can also be carried out in two steps effectively.In a first step, production still comprises the prepolymer of isocyanic ester and in second step, makes itself and more alcohol reactions.At this preferably, in a first step, single alcohol and isocyanate reaction.In the method, reactive diluent can add in the initial stage during producing prepolymer, or adds in second step.
The addition reaction that forms carbamate (randomly urea) can use suitable catalyzer to quicken in a manner known way, for example stannous octoate, dibutyl tin laurate or tertiary amine, for example dimethyl benzyl amine.Urethane acrylate as the reaction product preparation is protected by adding suitable inhibitor or oxidation inhibitor usually; to prevent too early and undesirable polymerization; for example phenols and/or hydroquinones and/or stable N--oxyl free radical and/or thiodiphenylamine or other free radical hold back agents, its amount is 0.0005 to 0.3 weight % based on resin melt in each case.The adding of these auxiliary substances can be before the reaction that forms polyurethane(s) (urea), simultaneously and/or carry out afterwards.
Except that discontinuous method, can also in tubular reactor, static mixer or extruder or reaction kneading machine, carry out described reaction.The short in these cases reaction times is favourable, wherein also can use higher temperature (80-220 ℃).
The present invention also provides powder coating, and it comprises
I) at least a powder paint substrate of the present invention,
Ii) randomly be different from i) other unsaturated base-materials, it has under the actinic radiation effect group (radiation cure groups) by polymerization and alefinically unsaturated compounds reaction,
Iii) common additive in auxiliary substance and the paint chemistry randomly, for example pigment, flowing regulator, air release agent, friction active additive and/or thixotropic agent and
Iv) at least a heat or photochemistry activatory free radical form agent.
The second-order transition temperature of powder coating of the present invention is 35 to 80 ℃, preferred 35 to 70 ℃, preferred especially 45 to 60 ℃.This depends on the character of structural constituent and the molecular weight and the consumption of reactive diluent to a great extent.Because, along with molecular weight improves, can also use more reactive diluent and therefore preparation have the resin of same glass transition temperature, so the amount of reactive diluent and therefore radiation curing functionality content can change by this way.
Powder paint compositions based on powder paint substrate of the present invention can also not use any other additive, process (in this case, described base-material will be identical with described coating composition) as the transparent powder paint of thermofixation.As the common additives in auxiliary substance and the coating process, for example pigment can be provided, titanium dioxide for example, flowing regulator, for example polybutyl acrylate or polysiloxane, air release agent, bitter almond oil camphor for example, friction active additive, for example fatty amine, thixotropic agent and/or other additives, and under 40 to 140 ℃, preferred 70 to 120 ℃ temperature, in forcing machine or kneading machine, introduce equably.Above-mentioned auxiliary substance and additive can be after described production immediately, at described production period or add at first in reaction mixture or the resin melt.
Remove the coarse particle part then in a manner known way with formed solid abrasive, and by screening, preferably remove granularity at least greater than those of 0.1 millimeter.
Can be according to the powder coating that the present invention produces by common powder coated method, for example electrostatic powder coating, frictional electrification coating or fluidized-bed apply, and are applied on the base material of wanting coated.Then under the effect of heating (for example by IR radiator) with the coating initial melted, and, do not adding under pigment or the similar substance situation, form transparent film.The temperature that needs be higher than 50 ℃, preferably be higher than 70 ℃, especially preferably be higher than 80 ℃.The curing of coating can be by being heated to 130 to 220 ℃, preferred 150 to 190 ℃ and/or for example carry out under the effect of ultraviolet radiation or electron beam emission at high-energy radiation.Electron emission produces by heat emission, as well known by persons skilled in the art, and quickens by means of potential difference.High-energy electron clashes into by titanium foil and is directed on the base-material that will be cured then.The General Principle of electrocuring is described in detail in " Chemistry ﹠amp; Technology of UV ﹠amp; EB Formulations forCoatings, Inks ﹠amp; Paints ", the 1st volume, PKT Oldring (editor), SITATechnology, London, Britain, 101-157 page or leaf, 1991.In electrocuring, do not need light trigger.
Passing through under the situation of solidified by ultraviolet ray radiation, light trigger is added coating composition as far as possible equably.Normally used compound if they do not have disadvantageous effect to for example unrestricted flow character of powder properties and shelf-life, then is to be suitable as light trigger.These example is 1-hydroxycyclohexylphenylketone, benzil dimethyl ketone acetal, perhaps-and under the situation of painted material-2-methyl isophthalic acid-(4-(methylthio group) phenyl-2-morpholino-acetone-1 or trimethylbenzoyl diphenyl phosphine oxide.
Light trigger, its weight with the coating based base-material are that the amount of 0.1 to 10 weight %, preferred 0.1 to 5 weight % is used, and can be used as independent material and use, and perhaps, because often have favourable synergistic effect, also mix mutually and use.
Under the thermofixation situation, this method can also be undertaken by adding thermolysis free radical formation agent.As well known by persons skilled in the art, the compound that is fit to is a peralcohol for example, peroxidation two acyls for example, benzoyl peroxide for example, alkyl hydroperoxide, diisopropyl benzene list hydroperoxide for example, the alkyl peroxy esters, t-butyl perbenzoate for example, dialkyl peroxide, ditertiary butyl peroxide for example, peroxy dicarbonate, double hexadecyl peroxy dicarbonate for example, inorganic peroxide, ammonium peroxydisulfate for example, Potassium Persulfate, or azo-compound, for example 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide], 1-[(cyano group-1-methylethyl) azo] methane amide, 2,2 '-azo two (N-butyl-2-methyl propanamide), 2,2 '-azo two (N-cyclohexyl-2-methyl propanamide), 2,2 '-azo two 2-methyl-N-[2-(1-hydroxybutyl)] propionic acid amide), 2,2 '-azo two 2-methyl-N-[2-(1-hydroxybutyl)] propionic acid amide and 2,2 '-azo two 2-methyl-N-[1, two (the methylol)-2-hydroxyethyls of 1-] propionic acid amide.Particularly suitable is the initiator that fusing point is lower than 130 ℃ solid form, and its transformation period be several minutes scopes, decomposition temperature is higher than 100 ℃.Also advantageously, the thermofixation for using initiator minimizes the concentration of stablizer.
Powder coating of the present invention is suitable for coated with the following base material of material: timber, metal, plastics, mineral substance and/or its coated base material, and perhaps by the base material that constitutes of any described material.Should should be mentioned that especially that at this following industrial coating uses: the MDF panel, comprise the high-grade goods of assembled in advance of for example electronic unit of temperature-sensing unit and the coating of furniture, coil, daily life goods, car body and its accessory.
The powder paint substrate of the present invention use that can also mutually combine, perhaps use with other base-materials that are generally used for the powder coating chemistry, for example use with polyester, polyacrylic ester, polyethers, polymeric amide and polycarbonate, they can also randomly comprise unsaturated group.The unsaturated group that is fit to is acrylate, methacrylic ester, fumaric acid class, Malaysia acids, vinyl and/or vinyl ether group.Determine quantitative ratio, two key density of the mixture that obtains are not less than 1.0 moles of two key per kilograms, because can not realize enough curing usually under the sort of situation.
Powder paint substrate can also be used for tackiness agent and sealing compositions.In these were used, by under the situation of solidified by ultraviolet ray radiation, prerequisite was bonded or at least a of two kinds of base materials of being sealed can see through ultraviolet radiation, promptly must be transparent usually.Under the situation of electron emission, must guarantee enough electronic transmissions.The base material that is fit to is made up of timber, metal, plastics, mineral substance and/or coated base material or the mixture of these base materials.
Powder paint substrate of the present invention also is suitable as component or the curing composition in thermoforming, injection moulding and the casting die.In this case, coated object is introduced into mould, and the distance that keeps between body surface and mould is not more than 1 centimetre, preferably less than 0.3 centimetre.Then powder paint substrate of the present invention is pressed into mould, preferably uses forcing machine, carry out thermofixation then and/or pass through radiation curing.
Embodiment
Embodiment
In following examples, all percentage ratios refer to weight percentage.
Glass transition temperature Tg is used differential scanning calorimeter, and (Giessen DE) measures in the temperature range of-15 ℃ to+150 ℃ (heating rate 10K/ minutes) for DSC 12E type, Metler-Toledo GmbH.
NCO content is by measuring according to the titration of DIN 53 185.
The embodiment of the invention
Embodiment 1a
At first with 482.22 isophorone diisocyanates, 0.28 gram 2,5-di-tert-butyl hydroquinone, 0.70 gram 2,6-di-tert-butyl-4-methy phenol, 0.35 gram Desmorapid Z (dibutyl tin laurate) (Bayer AG, Leverkusen, DE) and 0.70 gram p methoxy phenol add in the jar with plane lapping flange, and be heated to 90 ℃.Be metered into the mixture of 114.10 gram hydroxyethyl acrylate and 101.64 gram ethylene glycol then, with heat release; Temperature is maintained 90 ℃ at first, and when viscosity increases, be elevated to 130 ℃.After stirring 1h, NCO content reaches 0.43 weight %.With melt transfer to the dish in and the cooling.Second-order transition temperature unbodied, glass, brittle product is 73.7 ℃.
Embodiment 1b
Product and 15 gram Dipentaerythritols, five acrylate (Sartomer SR399 with 60 gram embodiment 1a, Cray Valley, Paris La Defense Cedex, France) have the reaction vessel of glass top and internal thermometer, and be heated to 120 ℃ initial the adding.After stirring 1h,, provide second-order transition temperature and be 51.3 ℃ product with the mixture cooling.
Embodiment 2a
At first with 459.30 isophorone diisocyanates, 0.28 gram 2,5-di-tert-butyl hydroquinone, 0.70 gram 2,6-di-tert-butyl-4-methy phenol, 0.35 gram Desmorapid Z (dibutyl tin laurate) (Bayer AG, Leverkusen, DE) and 0.70 gram p methoxy phenol add in the jar with plane lapping flange, and be heated to 90 ℃.Be metered into the mixture of 153.96 gram hydroxyethyl acrylate and 84.71 gram ethylene glycol then, with heat release; Temperature is maintained 90 ℃ at first, and when viscosity increases, be elevated to 120 ℃.After stirring 1h, NCO content reaches 0.23 weight %.With melt transfer to the dish in and the cooling.Second-order transition temperature unbodied, glass, brittle product is 59.0 ℃.
Embodiment 2b
Product and 7.5 gram Dipentaerythritols, five acrylate (Sartomer SR399 with 67.5 gram embodiment 2a, Cray Valley, Paris La Defense Cedex, France) have the reaction vessel of glass top and internal thermometer, and be heated to 120 ℃ initial the adding.After stirring 1h,, provide second-order transition temperature and be 48.5 ℃ product with the mixture cooling.
Embodiment 3
At first with 37.70 gram isophorone diisocyanates, 0.03 gram 2,5-di-tert-butyl hydroquinone, 0.076 gram 2,6-di-tert-butyl-4-methy phenol, 0.076 gram p methoxy phenol, 8.34 gram ethylene glycol, 5.95 gram vinylformic acid 2-hydroxyethyl esters and 22.79 gram Dipentaerythritols, five acrylate (Sartomer SR399, Cray Valley, Paris La Defense Cedex, France) the adding reaction vessel.Under agitation, temperature maintenance at 80 ℃ of following 1h, is maintained 90 ℃ of following 2h then.Add 0.04 gram Desmorapid Z (dibutyl tin laurate) then, and continue to stir other 30 minutes.At last, under agitation, kept 100 minutes, and continue to stir mixture heating up to 100 ℃.Obtained＜the NCO content of 0.07 weight %.Reaction mixture is kept so that cooling.Second-order transition temperature unbodied, glass, brittle product is 49.5 ℃.
Embodiment 4
At first with 33.36 gram isophorone diisocyanates, 0.03 gram 2,5-di-tert-butyl hydroquinone, 0.076 gram 2,6-di-tert-butyl-4-methy phenol, 0.076 gram p methoxy phenol, 8.44 gram ethylene glycol, 2.63 gram vinylformic acid 2-hydroxyethyl esters and 30.35 gram Dipentaerythritols, five acrylate (Sartomer SR399, Cray Valley, Paris La Defense Cedex, France) the adding reaction vessel.Under agitation, temperature maintenance at 80 ℃ of following 1h, is maintained 90 ℃ of following 2h then.Add 0.04 gram Desmorapid Z (dibutyl tin laurate) then, and continue to stir other 30 minutes.At last, under agitation, kept 100 minutes, and continue to stir mixture heating up to 100 ℃.Obtained＜the NCO content of 0.02 weight %.Reaction mixture is kept so that cooling.Second-order transition temperature unbodied, glass, brittle product is 52.3 ℃.
Embodiment 5-20
Following examples are with being prepared with embodiment 3 method the same with 4.The stablizer (2,5 di tert butylhydroquinone, 2,6 di tert butyl 4 methyl phenol, p methoxy phenol) and the catalyzer Desmorapid Z (dibutyl tin laurate) of same amount have been used.
Table 1: be used for base-material of the present invention based on the powder coating of urethane acrylate with reactive diluent.
| Embodiment | Glycol | Single alcohol | Vulcabond | Reactive diluent | ?Tg/℃ |
| ?5 ?6 ?7 ?8 ?9 ?10 ?11 ?12 ?13 ?14 ?15 ?16 ?17 ?18 ?19 ?20 | ?10.78gED ?10.18gED ?9.58gED ?8.97gED ?9.57gED ?10.17gED ?10.22gED ?9.35gED ?10.24gED ?10.17gED ?10.64gED ?12.67gED ?7.74gED ?10.07gPD ?11.04gPD ?9.33gED | ?7.68gHEA ?7.26gHEA ?6.82gHEA ?6.39gHEA ?6.82gHEA ?7.25gHEA ?3.19gHEA ?2.91gHEA ?3.19gHEA ?7.25gHEA ?3.32gHEA ?3.95gHEA ?2.70gHPA ?7.32gHEA ?8.03gHEA ?8.31gHEA | ?48.69gIPDI ?46.00gIPDI ?43.27gIPDI ?40.53gIPDI ?43.22gIPDI ?45.94gIPDI ?40.39gIPDI ?43.77gW ?40.50gIPDI ?45.94gIPDI ?42.07gIPDI ?39.26gTDI ?30.59gIPDI ?37.14gIPDI ?40.71gIPDI ?42.15gIPDI | ?7.63gTMPTA ?11.34gTMPTA ?15.12gTMPTA ?18.88gTMPTA ?15.17gTMPTA ?15.24gIDMA ?27.5gTMPTA ?18.75gTMPTA ?20.85gTPGDA ?11.43gIBOMA ?18.75gHDDA ?18.75gTMPTA ?33.75gDPEPA ?20.25gDPEPA ?15.00gDPEPA ?15.00gTCDDMA | ?64.7 ?56.6 ?49.0 ?41.4 ?51.8 ?55.0 ?49.8 ?49.1 ?53.6 ?57.0 ?52.8 ?44.0 ?50.7 ?42.7 ?54.6 ?50.6 |
Glycol: ED:1,2-ethylene glycol; PD:1, the 2-propylene glycol
Single alcohol: HEA: hydroxyethyl acrylate; HPA: vinylformic acid hydroxypropyl ester
Vulcabond: IPDI: isophorone diisocyanate=1-isocyanato--3-isocyanato-methyl-3,5,5-trimethyl-cyclohexane; W: two isocyanato-dicyclohexyl methyl hydrides (H12-MDI); TDI:2,4-and 2,80: 20 mixtures of 6-two isocyanato-toluene
Reactive diluent: TMPTA: Viscoat 295; TMPTMA: trimethylolpropane trimethacrylate; IDMA: isodecyl methacrylic ester; IBOMA: isobornyl methacrylic ester; HDDA: hexanediyl ester; DPEPA: Dipentaerythritol five acrylate; TCDDMA: tristane dimethanol dimethacrylate
Embodiment 21: polyacrylic ester and reactive diluent
At first with the 27.0 gram Jonacryl 587 (polyacrylate polyol of OH value 92, equivalent weight 609 and Tg=50 ℃, S.C.Johnson Polymer BV., Holland) and 3 gram trimethylolpropane trimethacrylates addings have the aluminium beaker of glass top and internal thermometer, and be heated to 120 ℃.After stirring 1h, mixture is cooled off.The second-order transition temperature of product is 38.3 ℃.
Embodiment 22a:2-step method
At first with 87.88 gram pentaerythritol triacrylates, 24.31 gram vinylformic acid hydroxypropyl esters, 0.13 gram 2,6-di-tert-butyl-4-methy phenol, 0.06 gram Desmofapid Z (dibutyl tin laurate) (Bayer AG, Leverkusen, DE) and 0.13 gram methyl p-toluenesulfonic esters add and have the three-necked flask of reflux exchanger and dropping funnel, and be heated to 50 ℃.In 20 minutes, drip 137.5 gram isophorone diisocyanates then, in the meantime with temperature maintenance at 55 ℃.Continue to stir other 3.5 hours, the NCO content of the liquid prepolymer that obtains is 14.1 weight %.
Embodiment 22b:2-step method
At first the product, 0.05 with 107 gram embodiment 22a restrains 2,5-di-tert-butyl hydroquinone, 0.09 gram 2,6-di-tert-butyl-4-methy phenol, 0.12 gram p methoxy phenol and 11.2 gram ethylene glycol add reaction vessel, described reaction vessel is made up of metal tin (preferred aluminium), the glass cover that has pressure compensation and be used for the hole of accurate glassed agitator, comes controlled temperature in the metal block by described jar is placed on.
Under agitation with mixture heating up to 90 ℃, keep 1h then.Add 0.09 gram Desmorapid Z (dibutyl tin laurate) then, and continue to stir other 2 hours at 120 ℃.Obtained the NCO content of 0.02 weight %.Reaction mixture is kept so that cooling.Second-order transition temperature unbodied, glass, brittle product is 37.0 ℃.
Embodiment 23 (using exemplary coating operation) from the base-material of embodiment 3
Use will be from the product cutting of embodiment 1b from the cutting machine of the model 10/6ROL of Alpine company.With this extractives of 97.0 weight %, flowing regulator Worl é eadd101 (the Worl é e-Chemie GmbH of 1.0 weight %, Lauenburg, DE) and 2.0 weight %Darocur , 1173 light triggers (Ciba Spezialit tenchemie GmbH, Lampertheim, DE) be weighed in the pre-mixing container, and Prism Pilot 3 premixers (pre-mixing sets 60 seconds/1500rpm) in pre-mixing.Extrude in APV forcing machine (HP 19PC) then, use following the setting: district 1: required value RT/ district 2: required value RT/ speed: the observed temperature of 300rpm/ melt: the utilization of 3.0/ average forcing machine ability is set in 55 ℃/metering: 55%.In refrigerator (Liebherr-Profi Line),, use Neumarm ﹠amp then 4 ℃ of section cool overnight that will obtain down; The Esser mill, model: ICM4:(classifier 15m/s; Rotor 60m/s) grinds, use 90 tm screen to sieve, and use ITW Gema fog gun (50-60mV; Pressure variations; The metering variable) sprays to immediately on the steel Q plate.With powder coating in circulated air oven 130 ℃ of following fusions 20 minutes, use IST S131P-7FO instrument (CK routine then; Belt speed 10m/min) with the described hot steel plate of UV photoirradiation.Film is hardening at once, estimates at cool to room temperature (RT) with after preserving 60 minutes.Film thickness is greater than 60 microns, granularity * 50%=30.3 micron.Use is immersed in the folded cotton wool of one in the acetone and estimates solvent resistance, and described cotton wool moves 100 doublestrokees with the pressure of about 1kg on film.Described film is anti-solvent and scratch.
Though above the present invention is described in detail for illustrative purposes, be to be understood that these details are just to illustrative purposes, and those skilled in the art can change it under the situation that does not deviate from spirit and scope of the invention, unless this is limited by claim of the present invention.
Claims (20)
1. powder paint substrate, this powder paint substrate has at least 35 ℃ second-order transition temperature, it comprises at least a following organic polymer that is selected from: polyurethane(s), polyester, polyacrylic ester, polyethers, polymeric amide, polycarbonate and above-mentioned mixture of polymers, and one or more radiation curing reactive diluents of at least 2 weight percentage.
2. the powder paint substrate of claim 1, the described organic polymer that wherein comprises at least a comprise can be under the actinic radiation effect group (radiation cure groups) by polymerization and alefinically unsaturated compounds reaction.
3. the powder paint substrate of claim 1, the second-order transition temperature of wherein said powder paint substrate is at least 42 ℃.
4. the powder paint substrate of claim 1, it comprises one or more radiation curing reactive diluents of 5-45 weight %.
5. the powder paint substrate of claim 1, wherein said reactive diluent is selected from Viscoat 295, trimethylolpropane trimethacrylate, Dipentaerythritol five acrylate and composition thereof.
6. the method for the powder paint substrate of production claim 1, it comprises and mixes following material:
A) one or more organic polymers, it is selected from polyurethane(s), polyester, polyacrylic ester, polyethers, polymeric amide, polycarbonate and composition thereof; With
B) one or more radiation curing reactive diluents of at least 2 weight %,
Wherein, component a) and b) composition and its mutual quantification selected, the second-order transition temperature of the powder paint substrate that obtains is at least 35 ℃.
7. powder coating, it comprises
I) powder paint substrate of at least a claim 1,
Ii) randomly be different from i) other unsaturated base-materials, it has under the actinic radiation effect group (radiation cure groups) by polymerization and alefinically unsaturated compounds reaction,
Iii) common additive in auxiliary substance and the paint chemistry randomly, its be selected from pigment, flowing regulator, air release agent, friction active additive and/or thixotropic agent and
Iv) at least a heat or photochemistry activatory free radical form agent.
8. the method for coated substrate, it comprises that the powder paint substrate with claim 1 is coated at least a portion of base material.
9. Accessory Right requires the coating that 1 powder paint substrate obtains.
10. use the base material of the paint coatings of claim 9.
11. the method for claim 8, wherein said base material are selected from timber, metal, plastics, mineral substance, coated base material and the base material of being made up of any described mixtures of material.
12. the method for coated substrate, it comprises that the powder coating with claim 7 is coated at least a portion of base material.
13. the method for claim 12, wherein said base material are selected from timber, metal, plastics, mineral substance, coated base material and the base material of being made up of any described mixtures of material.
14. the coating that the coating of Accessory Right requirement 7 obtains.
15. the base material that applies with the coating of claim 14.
16. the powder paint substrate of claim 2, the second-order transition temperature of wherein said powder paint substrate is at least 42 ℃.
17. the powder paint substrate of claim 2, it comprises one or more radiation curing reactive diluents of 5-45 weight %.
18. the powder paint substrate of claim 3, it comprises one or more radiation curing reactive diluents of 5-45 weight %.
19. the powder paint substrate of claim 2, wherein said reactive diluent are selected from Viscoat 295, trimethylolpropane trimethacrylate, Dipentaerythritol five acrylate and composition thereof.
20. the powder paint substrate of claim 3, wherein said reactive diluent are selected from Viscoat 295, trimethylolpropane trimethacrylate, Dipentaerythritol five acrylate and composition thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2003156041 DE10356041A1 (en) | 2003-12-01 | 2003-12-01 | Solid, radiation-curing binders with reactive diluents |
| DE10356041.6 | 2003-12-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1637092A true CN1637092A (en) | 2005-07-13 |
| CN100457842C CN100457842C (en) | 2009-02-04 |
Family
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|---|---|---|---|
| CNB2004100982745A Active CN100457842C (en) | 2003-12-01 | 2004-12-01 | Solid radiation-curable binders with reactive diluents |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US7514478B2 (en) |
| EP (1) | EP1538186B1 (en) |
| JP (1) | JP2005163043A (en) |
| CN (1) | CN100457842C (en) |
| AT (1) | ATE372362T1 (en) |
| CA (1) | CA2488658A1 (en) |
| DE (2) | DE10356041A1 (en) |
| ES (1) | ES2293151T3 (en) |
| HK (1) | HK1080103B (en) |
| MX (1) | MXPA04011818A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045033A (en) * | 2012-12-16 | 2013-04-17 | 青岛天人环境股份有限公司 | Composite coating |
| CN115279825A (en) * | 2019-12-19 | 2022-11-01 | 汉高股份有限及两合公司 | Silicone-free thermal interface material with reactive diluent |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7714062B2 (en) * | 2006-12-22 | 2010-05-11 | Carmen Flosbach | Thermal curable powder coating composition |
| US20090012202A1 (en) * | 2007-07-03 | 2009-01-08 | Henkel Corporation | Acrylated Urethanes, Processes for Making the Same and Curable Compositions Including the Same |
| JP6938848B2 (en) * | 2016-04-04 | 2021-09-22 | Dic株式会社 | (Meta) acrylate resin and printing ink |
| EP3272779A1 (en) | 2016-07-21 | 2018-01-24 | TIGER Coatings GmbH & Co. KG | Powder lacquer formulation |
| EP3299432A1 (en) * | 2016-09-26 | 2018-03-28 | HILTI Aktiengesellschaft | Dual component mortar composition and its use |
| EP3514206A1 (en) | 2018-01-19 | 2019-07-24 | TIGER Coatings GmbH & Co. KG | Thermoplastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5419895B2 (en) | 1973-07-27 | 1979-07-18 | ||
| DE3924679A1 (en) | 1989-07-26 | 1991-01-31 | Bayer Ag | USE OF POLYURETHANES CONTAINING (METH) ACRYLOYL GROUPS AS BINDERS FOR POWDER COATINGS |
| DE4228514A1 (en) | 1992-08-27 | 1994-03-03 | Hoechst Ag | Binder for powder coatings |
| DE4413436A1 (en) | 1994-04-18 | 1995-10-19 | Basf Lacke & Farben | Process for painting objects using radiation-curable powder coatings |
| GB9508458D0 (en) * | 1995-04-26 | 1995-06-14 | Ind Gmbh | Crystalline methacrylyl terminated polyesters |
| DE19621836A1 (en) * | 1996-05-31 | 1997-12-04 | Basf Lacke & Farben | Powder coating containing at least one binder containing hydroxyl groups and at least one crosslinking agent with free isocyanate groups, and its use for producing a multi-layer coating |
| JPH10231186A (en) * | 1997-02-24 | 1998-09-02 | Nof Corp | Production of cement-based inorganic material for surface coating |
| NL1007052C2 (en) * | 1997-09-17 | 1999-03-18 | Dsm Nv | Binder composition for powder paint formulations. |
| DE19939843A1 (en) | 1999-08-23 | 2001-03-01 | Bayer Ag | New binders for powder coatings containing (meth) acryloyl groups containing oligo- and polyurethanes |
| DE19947522A1 (en) * | 1999-10-02 | 2001-04-05 | Basf Ag | Polymerizable, solid aliphatic polyurethane with a sharp melting point, used in coating powder, e.g. for painting cars, based on linear aliphatic di-isocyanate, aliphatic diol or water and hydroxyalkyl acrylate |
| DE19947521A1 (en) * | 1999-10-02 | 2001-04-05 | Basf Coatings Ag | Solid mixture for use in coating, adhesive or sealant materials, e.g. for painting cars, contains a solid acrylic copolymer and another solid compound, both with groups containing UV-polymerizable bonds |
| DE19947523A1 (en) * | 1999-10-02 | 2001-04-05 | Basf Coatings Ag | Solid material for use in coating, adhesive and sealing materials, e.g. coating powder for painting cars, contains at least two structurally different light-activatable groups attached by urethane linkages |
| TWI238178B (en) * | 2001-03-13 | 2005-08-21 | Mitsubishi Gas Chemical Co | Method of producing powdery coating material |
| JP2003096401A (en) * | 2001-09-26 | 2003-04-03 | Dainippon Ink & Chem Inc | Active energy beam-curable powder coating and method for producing the same |
| DE10156322A1 (en) * | 2001-11-19 | 2003-06-05 | Bayer Ag | Solid radiation-curing binders |
| DE10163827A1 (en) * | 2001-12-22 | 2003-07-03 | Degussa | Radiation curable powder coating compositions and their use |
-
2003
- 2003-12-01 DE DE2003156041 patent/DE10356041A1/en not_active Withdrawn
-
2004
- 2004-11-18 DE DE200450004864 patent/DE502004004864D1/en active Active
- 2004-11-18 ES ES04027403T patent/ES2293151T3/en active Active
- 2004-11-18 AT AT04027403T patent/ATE372362T1/en active
- 2004-11-18 EP EP20040027403 patent/EP1538186B1/en active Active
- 2004-11-22 US US10/994,835 patent/US7514478B2/en active Active
- 2004-11-26 MX MXPA04011818A patent/MXPA04011818A/en active IP Right Grant
- 2004-11-29 CA CA 2488658 patent/CA2488658A1/en not_active Abandoned
- 2004-11-30 JP JP2004345935A patent/JP2005163043A/en active Pending
- 2004-12-01 CN CNB2004100982745A patent/CN100457842C/en active Active
-
2006
- 2006-01-03 HK HK06100012.8A patent/HK1080103B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045033A (en) * | 2012-12-16 | 2013-04-17 | 青岛天人环境股份有限公司 | Composite coating |
| CN115279825A (en) * | 2019-12-19 | 2022-11-01 | 汉高股份有限及两合公司 | Silicone-free thermal interface material with reactive diluent |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1538186B1 (en) | 2007-09-05 |
| JP2005163043A (en) | 2005-06-23 |
| US7514478B2 (en) | 2009-04-07 |
| HK1080103A1 (en) | 2006-04-21 |
| MXPA04011818A (en) | 2005-07-26 |
| DE502004004864D1 (en) | 2007-10-18 |
| EP1538186A1 (en) | 2005-06-08 |
| CA2488658A1 (en) | 2005-06-01 |
| US20050170185A1 (en) | 2005-08-04 |
| HK1080103B (en) | 2009-10-30 |
| ATE372362T1 (en) | 2007-09-15 |
| CN100457842C (en) | 2009-02-04 |
| ES2293151T3 (en) | 2008-03-16 |
| DE10356041A1 (en) | 2005-06-23 |
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